Derivative of piaselenol.



; entrain rr s rr oruicu.

EMIL FISCHER, OF BERLIN; GERMANY, ASSIGNOR 'IO FARBENFABRIKEN VORM.

FRIEDR. BAYER & 00.. MANY.

0F ELBERFELD, GERMANY, A CORPORATION OF GER- .DfiRIVATIVE OF PIASELENOL.

tor-zines.

No Drawing.

can be combined with selenious acid forming piaselenol:

/\ l th v (see Ber-ichte .(Zer 'Deuzjsohen Chemischen vGeseZZ-schaft vol; 22, 1889, 862 and 2895). Thehitherto described compounds of this class however are only-with great difficulty.

soluble in water and in alkali and are there- -fore unsuitable .for introduction into the blood circuit. I It has now been found that derivatives of pi-aselenol which are easily soluble in alkali and therapeutically valuable to; the treatment of tumors and for other purposes can be obtained by the action-of selenlous ac d on deriratiyes otaromatic ortho-diamins of an acid character, suchas oXy-, carboxylio,

sultonic acid or other alkali soluble derivatives of aromatic orthodiamins. These de-. rivatives-ozt the present invention have most probably the graphically represented formula B being an aromatic nucleus containing therein groups of an acid character.

. In order to lllustrat-e' the new process more fully the following examples are given, the

parts being by weight: I

Emample"1Pr0cluoti0n of parama'ypiaaeZen0Z.-l.2 diamino t-oxybenzene hydrochlorid (Journ. fair Pmkt. Chem/2'6 2, 43, 1891,13. 70) is dissolved in water and an Specification of Letters Patent.

Patented Sept. so, 1913.

Application filed January 29, 1913. Serial No. 744,876. 1

aqueous solution of the equii alent quantity of sodium hydroselenit is added to it. The oxypiaselenol which Very soon crystallizes from the mixture is collected on a filter and recrystallized from hot water with addition of a little animal charcoal. Ithas the formula and tormsyellowish-brown needles. having I no sharp melting point. On being heated in a capillary'melting pointtube it begins to sinter'being colored red below 200 C. and melts at about 209? C. with evolution of gas to av dark red liquid. It dissolves in the equivalent quantity'of alkali with a red to yellowish-red color according to the concentrationof the solution. The same oxypiaselenol is obtained whenfree 1.2-diamino-loxybenzene reacts in aqueous solution upon selenious acid.

Example 2--P1- 0 Zuctibn of 2.372ias'elen0ll-carbowyl'z'c aoz'd. 2.3ediauiinobenzoic acid hydrochlorid is dissolvedwater' and the calculated quantity v 1o elenious acid dissolved in water is ad ejreto. After a shorttime the 2.3} piaselenol-l-carboxylicv acid separates as a-flightefpinltcolored crystalline precipitate. It is collected *on a filter and recrystallized tromaxlarge quantity of hot Water. I melts-in the capillary who after previous sintering at "222-223? C. (coriz) IthasthefQ 'mula;

I q and yields easily: 'oliilole alkali. salts-Q; It is soluble in cold water only with very great difficulty. .Ei'enboilin water and alcohol dissolve it only with dificulty I-carbomylio acid.,'l:his; compound is pro-Q duced from the 3.4-d1am1nobenzoic acid hy 'drochloridin the same way as the isomeric compound described in Example 2 It is an almost colorless crystalline powder-and can small yellow needles is precipitated. These.

needles are on standing of; the mixture conbe purified by crystallization from hot dilute alcohol. It has no constant, melting point.

On being heated in ,the capillary tube -it darkens gradually while sintering at about 260 (1., and melts on quick heating at about 290 with decomposition. Its alkaline salts are easily soluble in water. Its solubility in othersolvents resembles the solubility of its 1somer.

Example 4Pr0ductz'on of 2.3-pz'aselmol- 4-methyZ-5-amino-I-sulfonio acid.---

' SO H NHJ LN 2.3.5triamino-t-methylbenzene-l-sulfonic acid or its hydrochlorid'is' dissolved in the calculated quantity (one or two molecules) of a highly diluted caustic soda lye, one molecule of acid sodium selenitfis added to this solution and then very slowly a' normal hydrochloric acid until a mass 'of verted into a )dirty yellow fine crystalline precipitate which is very diflicultly soluble in most. of the known organic solvents. It

is therefore advisable to convert the acid into its sodium salt. For this purpose the precipitate is dissolvedin hot dilute caustic soda solution, from which on cooling the sodium salt crystallizes in reddish-yellow needles. It can be purified by crystallization from water. The air-dry salt contains water of crystallization which can be completely removed 'by evaporation in mono at 100 C. The dried salt has the formula:

,, I I can mssena and is so soluble at ordinary temperature in water, that a 4: per cent. solution can be produced. The 2.3.5-triamino-a-methylbenzenel-sulfonic acid used as parent material is obtained byreducing'the azo-dye obtained from diazotized' para-nitranilin-ortho-sulfonic acid and 2.6-diaminotoluenel-sulfonic acid. The new acid thus obtained is rather difiicultlv soluble in cold water, it crystallizes in small needles and decomposes onbeing heated. It is easily soluble in alkalis and alkaline carbonates. The hydrochloric salt of the sulfonic acid dissolves rather easily in cold water whereby 1t 15 partly split into its components, the sulfonic acid crystallizing out.

'nOl-diSulfonic. acid separates.

7 described.

'crystallizing from yellowish-brown needles melting at about I 3 parts ofi 1 .2-diaminonaphthalene-5.7-

disulfonic acid hydrochlorid are dissolved in 50 parts of water and a concentrated solution of 2 parts of acid sodium selenit is added thereto. tion of barium chlorid is added by which means the barium salt of naphthopiaselelizes from boiling water in long slightly colored needles. The air-dry salt contains about 9 per cent. of water of crystallization,

which it'loses at 100 C. at a pressure of 10-20 mm. The dried salt has the formula: C H O N- S seBa.

' From. the barium salt the free sulfonic 2. As a new product the new para-oxypiaselenol having most probably the formula on- Lii water in the shape of 200-209" C. with evolution of gas; being soluble in dilute caustic alkali with a red to yellowish-red coloration; and being a therapeut'ically valuable remedy for the treatment of tumors, substantially' as described.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

. EMIL FISCHER. lVitnesses:

IVOLDEMAR Haurr, Ilsxnr H'AsrER.

After a short time a solu- It crystal- 

